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Identifying the Role of Dynamic Surface Hydroxides in the Dehydrogenation of Ti-Doped NaAlH4

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    Research Article

    Identifying the Role of Dynamic Surface Hydroxides in the Dehydrogenation of Ti-Doped NaAlH4
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2019, 11, 5, 4930–4941
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    https://doi.org/10.1021/acsami.8b17650
    Published January 11, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Solid-state metal hydrides are prime candidates to replace compressed hydrogen for fuel cell vehicles due to their high volumetric capacities. Sodium aluminum hydride has long been studied as an archetype for higher-capacity metal hydrides, with improved reversibility demonstrated through the addition of titanium catalysts; however, atomistic mechanisms for surface processes, including hydrogen desorption, are still uncertain. Here, operando and ex situ measurements from a suite of diagnostic tools probing multiple length scales are combined with ab initio simulations to provide a detailed and unbiased view of the evolution of the surface chemistry during hydrogen release. In contrast to some previously proposed mechanisms, the titanium dopant does not directly facilitate desorption at the surface. Instead, oxidized surface species, even on well-protected NaAlH4 samples, evolve during dehydrogenation to form surface hydroxides with differing levels of hydrogen saturation. Additionally, the presence of these oxidized species leads to considerably lower computed barriers for H2 formation compared to pristine hydride surfaces, suggesting that oxygen may actively participate in hydrogen release, rather than merely inhibiting diffusion as is commonly presumed. These results demonstrate how close experiment–theory feedback can elucidate mechanistic understanding of complex metal hydride chemistry and potentially impactful roles of unavoidable surface impurities.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b17650.

    • Experimental methods for sample preparation, characterization, and theoretical calculations; hydrogen mass spectrum; additional XPS spectra; STXM images and XAS spectra; XRD pattern of cycled NaAlH4; AIMD and NEB schematics; computed relative binding energies (PDF)

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    This article is cited by 21 publications.

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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2019, 11, 5, 4930–4941
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.8b17650
    Published January 11, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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